U.S. patent number 6,500,911 [Application Number 09/744,345] was granted by the patent office on 2002-12-31 for polyester diol and derived polyurethane and acrylic copolymer.
This patent grant is currently assigned to Daicel Chemical Industries, Ltd.. Invention is credited to Toshio Endo, Takuya Miho.
United States Patent |
6,500,911 |
Endo , et al. |
December 31, 2002 |
**Please see images for:
( Certificate of Correction ) ** |
Polyester diol and derived polyurethane and acrylic copolymer
Abstract
The invention provides polyester dials suitable for preparation
of polyurethanes, and provides polyurethanes derived therefrom. The
invention also provides spandex filaments prepared from these
polyurethanes, which exhibit improved elasticity, tensile strength,
and resistance to hydrolysis. The present invention also provides
dialkyl amino group-containing polyol additives having a high
solubility in dimethylacetamide solvent, which when incorporated
into a polyurethane protect the polyurethane and derived spandex
filaments from deterioration or discoloration, and confer an
improved modulus of elasticity. The polyurethanes and spandex
filaments of the invention provide fabrics having a soft feeling,
excellent hydrolysis resistance, wrinkle resistance, and adhesive
properties, and which are particularly suitable for preparation of
an artificial leather.
Inventors: |
Endo; Toshio (Ohtake,
JP), Miho; Takuya (Yamaguchi-ken, JP) |
Assignee: |
Daicel Chemical Industries,
Ltd. (Osaka, JP)
|
Family
ID: |
27527598 |
Appl.
No.: |
09/744,345 |
Filed: |
March 8, 2001 |
PCT
Filed: |
May 22, 2000 |
PCT No.: |
PCT/JP00/03265 |
PCT
Pub. No.: |
WO00/71598 |
PCT
Pub. Date: |
November 30, 2000 |
Foreign Application Priority Data
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May 20, 1999 [JP] |
|
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11-140727 |
May 20, 1999 [JP] |
|
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11-140739 |
May 20, 1999 [JP] |
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11-140745 |
May 20, 1999 [JP] |
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11-140749 |
Aug 18, 1999 [JP] |
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11-231307 |
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Current U.S.
Class: |
528/73; 428/364;
528/906 |
Current CPC
Class: |
C08G
18/4238 (20130101); C08G 18/4236 (20130101); C08G
18/4277 (20130101); D01F 6/70 (20130101); C08G
18/10 (20130101); C08G 18/0895 (20130101); C08F
220/34 (20130101); C08G 18/664 (20130101); C08G
18/4661 (20130101); C08G 18/10 (20130101); C08G
18/2865 (20130101); C08G 18/10 (20130101); C08G
18/3228 (20130101); Y10T 428/2913 (20150115); C08G
63/60 (20130101); Y10S 528/906 (20130101) |
Current International
Class: |
C08G
18/08 (20060101); C08F 220/34 (20060101); C08G
18/42 (20060101); C08F 220/00 (20060101); C08G
18/00 (20060101); C08G 18/10 (20060101); C08G
18/66 (20060101); D01F 6/58 (20060101); D01F
6/70 (20060101); C08G 18/46 (20060101); C08G
63/60 (20060101); C08G 63/00 (20060101); C08G
018/42 () |
Field of
Search: |
;528/73,906
;428/364 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 855 393 |
|
Jul 1998 |
|
EP |
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A-58059212 |
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Apr 1983 |
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JP |
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A-09316060 |
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Jul 1998 |
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JP |
|
A-10265557 |
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Oct 1998 |
|
JP |
|
A-11001822 |
|
Jan 1999 |
|
JP |
|
A-11292952 |
|
Oct 1999 |
|
JP |
|
Other References
International Search Report for Application No. PCT/JP00/03265,
Aug., 2000..
|
Primary Examiner: Gorr; Rachel
Attorney, Agent or Firm: Morgan & Finnegan, LLP
Claims
What is claimed is:
1. A polyurethane which is a copolymer of: (i) a polyester polyol
composition (X) which is a copolymer of a polyol (Al) having an
ultraviolet absorbing group and/or a lactone-modified polyol (A2)
derived therefrom, optionally one or more other polyol components
(A3), and adipic acid; and (ii) an organic diisocyanate (Y).
2. The polyurethane according to claim 1, wherein the polyol (A1)
is the compound represented by formula (1): ##STR6##
3. The polyurethane according to claim 1, wherein said lactone is
.epsilon.-caprolactone.
4. The polyurethane according to claim 2, wherein said lactone is
.epsilon.-caprolactone.
5. The polyurethane according to any one of claims 1-4, wherein the
number average molecular weight of the polyester diol ranges from
500 to 5,000.
6. The polyurethane according to any one of claims 3-4, wherein the
proportion of .epsilon.-caprolactone is between 20% and 95% by
weight of the polyester.
7. The polyurethane according to any one of claims 3-4, wherein the
proportion of .epsilon.-caprolactone is between 20% and 95% by
weigh of the polyester, and wherein the number average molecular
weight of the polyester diol ranges from 500 to 5,000.
8. The polyurethane according to any one of claims 1-4, wherein the
molar ratio {(A1)+(A2)}/{(A1)+(A2)+(A3)} of polyols in said polyol
composition is from 0.01 to 1.0.
9. The polyurethane according to claim 5, wherein the molar ratio
{(A1)+(A2)}/{(A1)+(A2)+(A3)} of polyols in said polyol composition
is from 0.01 to 1.0.
10. A spandex filament which comprises a polyurethane according to
any one of claims 1-4.
11. A spandex filament which comprises a polyurethane according to
claim 5.
12. A spandex filament which comprises a polyurethane according to
claim 6.
13. A spandex filament which comprises a polyurethane according to
claim 7.
14. A spandex filament which comprises a polyurethane according to
claim 8.
15. A spandex filament which comprises a polyurethane according to
claim 9.
Description
TECHNICAL FIELD
The present inventions No. 1 and No. 2 relate to a spandex filament
(a polyurethane elastic fiber) which is excellent in view of a
recovering ability of elasticity, high tensile strength and,
further, hydrolysis resistance, and relate to a polyurethane which
can provide thereof and, further, relate to a polyester diol.
The present invention No. 3 relates to a spandex filament which is
excellent in view of hydrolysis resistance and a novel polyurethane
which can provide thereof.
The present invention No. 4 relates to a polyurethane which is
excellent in weatherability. In more detail, it relates to a
polyurethane having a (washing resistance) property in which the
weatherability does not almost lower even though being repeatedly
washed, and relates to a spandex filament comprising the
polyurethane.
The present invention No. 5 relates to a dialkyl amino
group-contained acrylic-based copolymer which is useful as a high
molecular-state amine stabilizer for a polyurethane. In more
detail, the present invention relates to an improvement of the
amine stabilizer for, particularly, a polyurethane/spandex filament
and a film. It is to be noted that the terminology "spandex"
employed in the No. 5 means a synthesized elastomeric composition
having a long chain which contains at least 85% by weight of a
segment-state polyurethane.
The present invention No. 6 relates to a polyurethane having
properties which are excellent in a soft feeling, hydrolysis
resistance, wrinkle resistance, and an adhesive property and,
particularly, it is excellent as an artificial leather.
TECHNICAL BACKGROUND
In the present inventions No. 1 and No. 2, a polyurethane having a
linear-state structure is obtained by allowing to react a long
chain diol having hydroxyl groups at both terminals with an organic
diisocyanate and a diol or a diamine, etc. which is named a
relatively low molecular weight chain extender having two active
hydrogens. Concerning a recovering ability of elasticity and
hydrolysis resistance in thus-obtained polyurethane, various
attempts for an improvement have been proposed. As described in
JP-A-58059212 Official Gazette, although a polyurethane using a
polyethylene glycol adipate polyester is excellent in a recovering
ability of elasticity, it is poor in hydrolysis resistance.
Further, although a 1,4-butylene glycol adipate polyester has a
certain extent of hydrolysis resistance, a recovering ability of
elasticity is poor in a polyurethane therefrom. Still further,
although a polyurethane prepared from a polycaprolactone polyol is
excellent in hydrolysis resistance, weatherability, and heat
resistance, it is poor in a recovering ability of elasticity. In
the JP-A-58059212 Official Gazette, there is described a technology
using a specified polycaprolactone polyester polyol obtained by an
esterification reaction of a polyester polyol synthesized by a
dehydration esterification of neopentylglycol with adipic acid with
.epsilon.-caprolactone as a method for solving a drawback of a
polycaprolactone-based polyurethane. Further, in the JP-A-11001822
Official Gazette, there are disclosed polyurethane elastic fibers
which are excellent in alkali-hydrolysis resistance in which there
are employed 2-n-butyl-2-ethyl-1,3-propane diol and
2,2-diethyl-1,3-propane diol as a diol component which constructs a
polyester polyol.
In relation to the present invention No. 2, in JP-A-63097617
Official Gazette, there is described a spandex filament, etc. which
is improved in bacteria resistance, and which is prepared from a
poly(2,2-dimethyl-1,3-propane dodecanedioate).
However, since the recovering ability of elasticity and hydrolysis
resistance are not always sufficient in the polyurethane described
in the JP-A-58059212 Official Gazette, there is desired a
polyurethane in which those are improved. Further, although the
polyurethane elastic fibers in the JP-A-11001822 Official Gazette
are excellent in hydrolysis resistance, it is desired to further
improve a recovering ability of elasticity and strength. Still
further, in the spandex filaments described in the JP-A-630978617
Official Gazette, there is desired a further improved strength.
In relation to the present invention No. 3, a polyurethane having a
linear structure is obtained by allowing to react a long chain diol
having hydroxyl groups at both terminals with an organic
diisocyanate and a relatively low molecular weight diol or diamine
which is named a chain extender having two active hydrogens.
For improvement of characteristics of thus-obtained polyurethane,
various proposes have been made. For example, in the JP-A-11001822
Official Gazette, there are disclosed polyurethane elastic fibers
which are excellent in alkali hydrolysis resistance in which there
are employed 2-n-butyl-2-ethyl-1,3-propane diol and
2,2-diethyl-1,3-propane diol as a diol component which constructs a
polyester polyol.
Further, in JP-A-63097617 Official Gazette, there is described a
spandex filament, etc. which is improved in bacteria resistance,
and which is prepared from a poly(2,2-dimethyl-1,3-propane
dodecanedioate).
However, although the polyurethane described in the JP-A-11001822
Official Gazette is excellent in a certain extent of hydrolysis
resistance, there is further desired an improvement.
Also in the spandex filament described in the JP-A-63097617
Official Gazette, it is in the same situation.
The polyurethane having a linear structure in relation to the
present invention No. 4 is prepared by allowing to react a long
chain diol having hydroxyl groups at both terminals with an organic
diisocyanate and a relatively low molecular weight diol or diamine
which is named a chain extender having two active hydrogens.
Thus-obtained polyurethanes are employed for a variety of uses, for
example, a thermoplastic elastomer, a hard or soft urethane foam,
an adhesive, an artificial leather, a synthetic leather, a coating,
and an elastic fiber (a spandex filament), etc.
The polyurethanes are naturally excellent in weatherability
(including a light resistance) and durability and, in order to
further give weatherability, there are employed publicly-known
ultraviolet ray absorbents, for example, benzotriazoles such as
2-(2'-hydroxy-5'-methylphenyl)benzotriazole and
5-chloro-2-(2'-hydroxy-3', 5'-di-t-butylphenyl)benzotriazole, and
benzophenones such as 2,4-dihydroxybenzophenone and
2-hydroxy-4-octyloxybenzophenone.
However, since the conventional ultraviolet ray absorbents are a
low molecular weight compound having a low boiling point, the
addition thereof to a polyurethane causes various
inconveniences.
For example, the addition of a large amount of the ultraviolet ray
absorbents causes a phase separation, resulting in that whiteness
and mechanical strength are lowered in the polyurethane.
Therefore, although the ultraviolet ray absorbent is added as a
small amount as possible and, in the case, light resistance is not
elevated until a satisfying extent in the polyurethane. Further,
since the ultraviolet ray absorbent is lost by evaporation or
decomposed during processing or molding, or it oozes out on the
surface of a molded article, it becomes impossible to give a stable
light resistance over a long time of period. Still further, when a
spandex filament product is repeatedly washed, the ultraviolet ray
absorbent is removed from the product, and an effect is gradually
reduced.
By the way, an object is not limited to the polyurethane, in order
to solve the above-described drawbacks, there is tried an attempt
(JP-A-60038411 Official Gazette, JP-A-62181360 Official Gazette,
and JP-A-03281685 Official Gazette, etc.) for giving a
polymerizable double bond such as vinyl group to the
above-described ultraviolet ray absorbent, for highly-polymerizing
the absorbent to improve a compatibility with a variety of resins,
and for preventing evaporation, thermal decomposition, and
bleeding, etc. of the ultraviolet ray absorbent.
However, these ultraviolet ray absorbable polymers also have a
drawbacks as described below, and room for an improvement remains.
That is, although thermoplastic resins such as thermoplastic
polyurethane resins have an exceedingly high mechanical strength
and those are widely employed as a various molding materials, since
the thermoplastic polyurethane resins have a drawback of a decline
in the mechanical strength by decomposition due to alkali
components, and there has been desired an improvement of chemical
resistance such as an alkali resistance and solvent resistance.
It is to be noted that JP-A-10265557 Official Gazette describes a
lactone-modified polyol made from a polyol having an ultraviolet
ray absorbable group. However, it does not describe the use thereof
as a constructing component for a polyester diol which is a raw
material for a polyurethane.
In relation to the present invention No. 5, a segment-state
polyurethane is well known, which is prepared by forming an
isocyanate-terminated polymer through allowing to react a high
molecular weight diol (most of those are a polyether glycol or a
polyester glycol) with an organic diisocyanate, and by
chain-extending through allowing to react thereof with a diamine or
a diol.
The terminology "fiber" includes staple fibers and continuous
filaments.
U.S. Pat. No. 3,428,711 by Hunt discloses the use of a high
molecular weight tertiary aminoalkyl acrylate and methacrylate for
stabilizing a segment-state polyurethane, and a large commercial
use is found out as fibers for spandex. Hunt discloses a large
amount of such additives. A preferred stabilizer disclosed by Hunt
is a copolymer of diisopropyl amino ethylmethacrylate (hereinafter,
named "DIPAM") which has a steric hindrance with
n-decylmethacrylate (hereinafter, named "DM"). The copolymer
(hereinafter, named "poly(DIPAM/DM)") provides a polymer for a
spandex which has a large resistance to deterioration by exposure
to chlorine than a similar amine which does not have a steric
hindrance.
Additives containing a tertiary amino group having a high molecular
weight and a steric hindrance are useful for preventing
deterioration and discoloration of for a spandex polymer. However,
the additives are occasionally cause a problem in the preparation
and/or a change to worse of properties in a fiber prepared from the
spandex polymer. For example, the use of the poly(DIPAM/DM)
additives causes a certain kind of a problem in the case of
dry-spinning a filament from a spandex polymer solution. Dimethyl
acetoamide (hereinafter, named "DMAc") is a solvent to be most
preferably employed for the preparation of the spandex polymer
solution. The poly(DIPAM/DM), an antioxidant, and other additives
such as pigments are usually changed to a slurry together with the
DMAc, followed by being mixed with the spandex polymer solution
prior to spinning. However, such the slurry usually prepared at
room temperatures occasionally causes a phase-separation in the
case that a high molecular weight amine lacks a solubility to the
DMAc solvent. The phase-separation has a possibility of causing
aggregation of the additives, a problem during spinning and/or an
uniform distribution of the additives into a solution for spinning
and filaments spun therefrom. That is, the polymer for spandex
containing the poly(DIPAM/DM) or the (DPAM) additives adversely
affects to a preparation step because of inferiority of solubility
to solvent when being spun, and it causes a certain kind of
drawback to elasticity in filaments prepared from the spandex
polymer, that is, an undesired decline (that is, permanent
extension (set)) of elasticity in the spandex filaments made by
dry-spinning.
A great parts of high molecular weight tertiary
aminoalkyl(meth)acrylate additives have any one of or both
drawbacks.
On the other hand, JP-A-02086655 by Roden et al suggests the DIPAM
and a hydroxybutyl acrylate- or methacrylate-based copolymer in
order to provide an additive containing a high molecular weight
tertiary amine having a steric hindrance which is employed for a
spandex polymer.
However, in the copolymer described in the JP-A-02086655, although
it suppresses a manifestation of the decline (that is, permanent
extension (set)) in elasticity related to the use of already known
additives containing a high molecular weight tertiary amino group
having a steric hindrance to a certain extent, it is not always
sufficient in solubility to the DMAc solvent, and it still has a
possibility of a manifestation of the decline in elasticity.
In relation to the present invention No. 6, it is usually and
widely known that an artificial leather is obtained by processing
of adding a variety of polymer compounds to a nonwoven sheet-like
material primarily composed of an ultra-fine fiber. As the polymer
compounds in the case, there are employed many elastic polymer
compounds such as a polyurethane, etc. in order to obtain physical
properties such as a soft and elastic feeling as an artificial
leather, durability, and dimensional stability. And, the elastic
polymer compounds are coated on a nonwoven sheet-like material as a
solution dissolved in an organic solvent, and then, very often
moisture-solidified.
On the other hand, since the organic solvent employed in the case
is often a substance which is very inflammable and highly toxic,
many attention must be paid when recollecting the solvent for
preventing a fire and a danger by toxicity. Further, there is a
drawback that the solvent is expensive and many costs are required
for recollecting it from a diluted aqueous solution.
Because of the various drawbacks, a variety of investigations are
made for shifting from an organic solvent type to a water-based
emulsion in the elastic polymer compound for coating on the
nonwoven sheet-like material. However, it is the existing state
that there is not still obtained an artificial leather having a
satisfying a feeling and physical properties using a water-based
emulsion.
In general, a polyurethane having a linear structure is obtained by
allowing to react a long chain diol having hydroxyl groups at both
terminals with an organic diisocyanate and a relatively low
molecular weight diol or diamine which is named a chain extender
having two active hydrogens, and a technical background relating to
the polyurethane is as described in technical background relating
to the present inventions No. 1 and No. 2.
DISCLOSURE OF THE INVENTION
Accordingly, purpose of the present inventions No. 1 and No. 2 is
to provide a spandex filament which is excellent in recovering
ability of elasticity, strength, and hydrolysis resistance, a
polyurethane which provides it, and a polyester diol which provides
thereof.
The present inventors found out that the above-described problems
can be solved by the use of a polyester diol obtained from a
specified branched aliphatic diol, e-caprolactone, and adipic acid,
which is a raw material for a polyurethane, and the present
invention No. 1 has been completed.
Further, the present inventors found out that the above-described
problems can be solved by the use of a polyester diol obtained from
a specified branched aliphatic diol, .epsilon.-caprolactone, and an
aliphatic dicarboxylic acid having a carbon number of 10-12, and
the present invention No. 2 has been completed.
That is, according to the present invention No. 1, as (1), there is
provided a polyester diol containing at least one diol selected
from the group consisting of 2-n-butyl-2-ethyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol,
.epsilon.-caprolactone, and adipic acid as constructing
components.
Further, as (2), there is provided a polyester diol as described in
the (1), in which a number average molecular weight ranges in
500-5,000.
Still further, as (3), there is provided a polyester diol as
described in the (1) or (2), in which (the content of a
constructing unit polyester)/(the content of constructing unit of
.epsilon.-caprolactone) ranges in 5/95-80/20 (weight ratio), and
the polyester is composed of at least one diol selected from the
group consisting of 2-n-butyl-2-ethyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol, and
adipic acid.
Also, as (4), there is provided a polyurethane obtained from a
polyester diols as described in any one of the (1)-(3) and an
organic diisocyanate.
And also, as a (5), there is provided a spandex filament which
comprises the polyurethane in the (4).
Further, according to the present invention No. 2, as (1), there is
provided a polyester diol containing a branched aliphatic diol,
.epsilon.-caprolactone, and an aliphatic dicarboxylic acid having a
carbon number of 10-12 as constructing components.
Further, as a (2), there is provided a polyester diol as described
in the (1), in which a number average molecular weight ranges in
500-5,000.
Still further, as a (3), there is provided a polyester diol as
described in the (1) or (2), in which (the content of a
constructing unit polyester)/(the content of constructing unit of
.epsilon.-caprolactone) ranges in 5/95-80/20 (weight ratio), and
the polyester is composed of a branched diol and an aliphatic
dicarboxylic acid having a carbon number of 10-12.
Also, as (4), there is provided a polyurethane obtained from a
polyester diols as described in any one of the (1)-(3) and an
organic diisocyanate.
And also, as a (5), there is provided a spandex filament which
comprises the polyurethane described in the (4).
Purpose of the present invention No. 3 is to provide a spandex
filament which is particularly excellent in view of hydrolysis
resistance, and a polyurethane which provides thereof.
The present inventors found out that the above-described problems
in the present invention No. 3 can be solved by the use of a
polyester diol containing a specified diol as a raw material for
the polyurethane, and the present invention has been completed.
That is, according to the present invention No. 3, as (1), there is
provided a polyurethane obtained by allowing to react a polyester
diol containing 2,4-diethyl-1,5-pentanediol as a constructing
component with an organic diisocyanate.
Further, as (2), there is provided a polyurethane described in the
(1), in which a number average molecular weight ranges in
500-5,000.
Still further, as (3), there is provided a spandex filament which
comprises the polyurethane described in the (1) and (2).
Purpose of the present invention No. 4 is to provide a spandex
filament in which there is improved washing resistance as a
weatherability, and to provide a polyurethane which provides
thereof.
The present inventors found out that the above-described problems
can be solved by the use of a polyester diol in which a polyol
component (A) is composed of a polyol (A1) having an ultraviolet
ray-absorbable group or a lactone-modified polyol (A2) therefrom
and other polyol (A3) as a raw material for the polyurethane, and
the present invention has been completed.
That is, according to the present invention No. 4, as (1), there is
provided a polyurethane obtained from a polyetherpolyol (X)
containing a polyol component (A) composed of a polyol (A1) having
an ultraviolet ray-absorbable group or a lactone-modified polyol
(A2) therefrom and other polyol components (A3), adipic acid (B),
and an organic diisocyanate (Y).
Further, as (2), there is provided a polyurethane described in the
(1), in which the polyol (A1) having an ultraviolet ray-absorbable
group is a compound represented by formula (1). ##STR1##
Still further, as (3), there is provided a polyurethane described
in the (1) or (2), in which the lactone is
.epsilon.-caprolactone.
Also, as (4), there is provided a polyurethane described in any one
of the (1)-(3), in which a number average molecular weight of the
polyester polyol ranges in 500-5,000.
And also, as (5), there is provided a polyurethane described in any
one of the (1)-(4), in which (a constructing unit content of the
polyester)/(the content of constructing unit of a lactone) is
5/95-80/20 (weight ratio), and the polyester is composed of the
polyol compound (A) and adipic acid.
And also, as the present invention (6), there is provided a
polyurethane as described in any one of embodiments (1)-(5), in
which a molar ratio of constructing unit content in the polyol
{(A1)+(A2)}/{(A1)+(A2)+(A3)} ranges from 0.01 to 1.0.
And also, as the present invention (7), there is provided a spandex
filament which comprises the polyurethane described in any one of
the (1)-(6).
Purpose of the present invention No. 5 is to provide a tertiary
amino group-contained additive which is employed for a spandex
polymer, in which solubility into DMAc which is a solvent is
higher, by which the spandex polymer is protected from
deterioration and discoloration, and in which a decrease of
elasticity (permanent extension (set)) is further improved in
relation to the use of an already-known tertiary amino
group-contained additive having a high molecular weight and steric
hindrance, to provide a polyurethane composition and a spandex
composition containing the additives.
The present inventors, as an intensive investigation for solving
the above-described problems, found out that an acrylic-based
copolymer has a high solubility into DMAc which is a solvent and
has an exact effect, and the above-described problems can be
solved, which contains a novel tertiary amino group formed by a
dialkylaminomethyl(meth)acrylate and a reactive monomer having a
specified structure which are an essential copolymerizable
component, and the present invention No.5 has been completed.
That is, according to the present invention No. 5, as (1), there is
provided a dialkylamino group-contained acrylic-based copolymer
formed by an essential copolymer component which includes a
dialkylaminoethyl(meth)acrylate represented by a general formula
(1) described below and a reactive monomer represented by a general
formula (2) described below.
(in the formula, R is a hydrogen atom or a methyl group, R.sup.0 is
an alkyl group having a carbon atom number of 1-4)
(in the formula, R is a hydrogen atom or a methyl group, x pieces
of R.sup.1 and R.sup.2 are independently a hydrogen atom or an
alkyl group having a carbon atom number of 1-12, respectively, and
n pieces of ring-opened lactone chains may be identical or
different from each other. x is an integer of 4-7, and an average
value of n is 1-5)
Further, as (2), there is provided a polyurethane composition
characterized by containing a dialkylamino group-contained
acrylic-based copolymer described in the present invention (1).
Still further, as (3), there is provided a polyurethane composition
as described in the invention (3), in which the content of the
dialkylamino group-contained acrylic-based copolymer is 0.5-10% by
weight.
Also, as (4), there is provided a spandex composition containing a
dialkylamino group-contained acrylic-based copolymer as described
in the invention (1).
Also, as (5), there is provided a spandex composition as described
in the invention (4), in which the content of the dialkylamino
group-contained copolymer is 0.5-10% by weight.
Purpose of the present invention No. 6 is to provide a polyurethane
which provides an artificial leather which is excellent in a
recovering ability of elasticity, strength, and hydrolysis
resistance, that is, which satisfies hydrolysis resistance, wrinkle
resistance, an adhesive property, and a feeling.
The present inventors, as a result of an intensive investigation
for solving the purpose in the present invention No. 6, have
attained to the present invention.
That is, according to the present invention No. 6, as (1), there is
provided a polyester diol containing at least an aliphatic
dicarboxylic acid, an aliphatic diol, and e-caprolactone as
constructing component units.
Further, as (2), there is provided a polyester diol as described in
the (1), in which a number average molecular weight of the
polyester polyol ranges in 500-5,000.
Still further, as (3), there is provided a polyester diol as
described in the (1) or (2), in which (the content of a polyester
constructing unit composed of an aliphatic diol and an aliphatic
dicarboxylic acid having a carbon number of 9-12)/(the content of
.epsilon.-caprolactone constructing unit) ranges in 5/95-80/20
(weight ratio).
Also, as (4), there is provided a polyurethane obtained from a
polyester diol as described in any one of the (1)-(3) and an
organic diisocyanate.
And also, as (5), there is provided a polyurethane described in the
(4) for an artificial leather.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments for carrying out the present invention No.
1 and the present invention No. 2 will be illustrated one after
another.
The present invention No. 1 will be illustrated
The diol to be employed in the present invention is a specified
diol, that is, at least one diol selected from the group of
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and
2,4-diethyl-1,5-pentanediol. These may be employed solely,
respectively, or in mixing of two kinds. Further, within a range in
which an effect by the present invention is not deteriorated, other
diol components can be employed. As such the diol compounds, there
are enumerated ethylene glycol, propylene glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol,
3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol,
dipropylene glycol, and 1,4-cyclohexane dimethanol, etc.
Although adipic acid is employed as an acid component for the
polyester diol in the present invention, within a range in which an
effect by the present invention is not deteriorated, there can be
employed other acid components, for example, aliphatic or aromatic
dicarboxylic acids such as glutaric acid, pimelic acid, sberic
acid, azelaic acid, sebasic acid, dodecanoic acid, 1,11-undecane
dicarboxylic acid, terephthalic acid, isophthalic acid, and
5-sulphosodium isophthalic acid. The other acid components may be
employed solely or even as a mixture of two or more kinds together
with adipic acid. It is to be noted that the acid components which
are a raw material may be employed in the form of an ester
derivative or an acid anhydride. In the diol relating to the
present invention, other constructing components are
.epsilon.-caprolactone and, within a range in which an effect by
the present invention is not deteriorated, there may be even
employed a methylated .epsilon.-caprolactone such as
monomethyl-.epsilon.-caprolactone, and
trimethyl-.epsilon.-caprolactone, .gamma.-butyrolactone, and
.delta.-varelolactone as auxiliary components for
.epsilon.-caprolactone.
A method for the preparation of the polyester diol in the present
invention is not particularly limited and, publicly-known methods
can be applied. For example, it can be prepared according to a
method described in the JP-A-58059212 Official Gazette. That is, it
can be prepared through (a one-pot method) a dehydration
esterification and a ring-opening reaction, and a
transesterification by heating after mixing the above-described
diols, .epsilon.-caprolactone, and adipic acid. Otherwise, it can
be also prepared by mixing and heating a polyester diol obtained by
a dehydration esterification of a diol with adipic acid with a
polycaprolactone polyol which is synthesized by allowing to conduct
a ring-opening polymerization of .epsilon.-caprolactone with a
polyvalent alcohol, followed by a transesterification thereof.
Further, it can be also prepared by ring-opening polymerization of
.epsilon.-caprolactone with a polyester polyol having a low
molecular weight. Of those, the one-pot method is preferred owing
to be convenient.
The reactions can be conducted at 130-240.degree. C., preferably
140-230.degree. C. from a viewpoint of preventing discoloration and
from a viewpoint of preventing a decomposition reaction of
.epsilon.-caprolactone.
In the reactions, catalysts are usually employed in 0.05-1000 ppm
by weight, preferably 0.1-100 ppm by weight based on total
monomers. As the catalysts, there can be employed organic titanium
compounds such as tetrabutyl titanate and tetrapropyl titanate, tin
compounds such as dibutyltin laurate, tin octylate, dibutyltin
oxide, stannous chloride, stannous bromide, and stannous
iodide.
The reactions can be preferably conducted while streaming an inert
gas such as nitrogen gas from a viewpoint of preventing
discoloration of a desired product obtained.
As content of constructing unit of the polyester diol in the
present invention, respective raw materials are employed in a range
of a proportion so that (content of constructing unit of the
polyester)/(content of constructing unit of .epsilon.-caprolactone)
becomes a range of 5/95-80/20 (weight ratio), which is composed of
at least one kind selected from the group consisting of
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and
2,4-diethyl-1,5-pentanediol and adipic acid. Also in the case that
a poly-.epsilon.-caprolactone is employed, it is the same. In
thus-obtained polyester diol, a number average molecular weight
ranges in 500-5,000, preferably 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
A polyurethane is prepared from the polyester diol obtained as
described hereinabove and an organic diisocyanate. As a method for
the preparation of the polyurethane, there are enumerated
publicly-known methods, for example, the methods described in the
JP-A-58059212 Official Gazette and JP-A-11001822 Official Gazette
and, it may be conducted according to these. That is, there are a
one-shot method in which a polyester diol, a low molecular weight
diol or diamine, etc. which are a chain extender, and an organic
diisocyanate are allowed to collectively react under the presence
or absence of solvents and a prepolymer method in which a
prepolymer is prepared by allowing to previously react a polyester
diol with an organic diisocyanate, and then, a low molecular weight
diol is allowed to react under the presence or absence of
solvents.
A melting polymerization method which is conducted under the
absence of solvents is preferred from a viewpoint of costs. In the
case, a formulation ratio of raw materials is 0.5-1.5, preferably
0.8-1.2 as (NCO group in the organic diisocyanate)/(total OH group
in the polyester diol and a low molecular weight diol). As the
solvents, there are enumerated toluene, xylene, ethyl acetate,
butyl acetate, methylethyl ketone, dimethyl formamide, and
tetrahydrofran, etc.
As the organic diisocyanate to be employed in the present
invention, there are enumerated 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, p-phenylene diisocyanate,
4,4'-diphenylmethane diisocyanate, m-phenylene diisocyanate,
hexamethylene diisocyanate, tetramethylene diisocyanate,
2,4-naphthalene diisocyanate, 4,4'-diphenylene diisocyanate,
p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diisocyanate
dicyclohexane, and isophorone diisocyanate, etc. These may be even
employed solely or in combination of two or more kinds.
As the above-described low molecular weight diol which is a chain
extender, there can be employed the diols to be employed in the
present invention or the diol compounds which can be employed
together as described hereinabove.
As the diamine which is a chain extender, there can be employed
ethylenediamine, hydrazine, isophoronediamine, metaphenylene
diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulphone,
and 3,3'-dichloro-4,4'-diaminodiphenylmethane, etc.
The polyurethane obtained by the above-described methods is
employed in a variety of uses in which a usual polyurethane is
employed, for example, a thermoplastic elastomer, a hard or soft
urethane foam, an adhesive, an artificial leather, and coating,
etc., and particularly, it is preferred to employ for a spandex
filament.
As a spinning method for obtaining a spandex filament from the
polyurethane in the present invention, there can be employed
publicly-known methods, for example, a dry-spinning method, a
wet-spinning method, and a melt-spinning method, etc. Of the
methods, the melt-spinning method is preferred from a viewpoint of
costs.
Further, there is obtained a filament having a further high
physical properties by heat treatment of an elastic filament after
spinning.
In the spandex filament of the present invention, there can be also
optionally added an antioxidant such as a phenol-derivative, an
ultraviolet ray absorbent such as a substituted benzotriazole, and
an anti-blocking agent such as a higher fatty acid metal salt and a
silicone compound, etc.
The spandex filament provided by the present invention is excellent
in a recovering property of elasticity, strength, and hydrolysis
resistance, and it is employed in a general use form for a spandex
filament, that is, a mix-knitting and mix-weaving with a nylon and
cotton, etc. Particularly, in the case that the cotton is employed
as a material for mixing, it shows an excellent hydrolysis
resistance even through post treatment steps after mix-knitting and
mix-weaving, that is, a boiling-off step, a bleaching step, and a
mercerization step, etc. in which it is treated at a high
temperature under an acid or alkali atmosphere.
Hereinafter, there are illustrated embodiments for carrying out the
present invention No. 2.
As the branched diols to be employed in the present invention, for
example, there are enumerated 1,2-propylene glycol, 1,3-butylene
glycol, 2-methyl-1,3-propane diol, neopentyl glycol,
3-methyl-1,5-pentane diol, 2-n-butyl-2-ethyl-1,3-propane diol,
2,2-dimethyl-1,3-propane diol, 2,2-diethyl-1,3-propane diol,
2,4-diethyl-1,5-pentane diol, 1,2-hexane glycol, and 1,2-octyl
glycol, etc. These may be employed solely or even in mixing of two
or more kinds. Further, within a range in which an effect by the
present invention is not deteriorated, other diol components can be
also employed as auxiliary components. As such the diol compounds,
there are enumerated aliphatic diols not having branches, for
example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol,
1,6-hexanediol, 1,8-nonanediol, and diethylene glycol, etc.
As an acid component for the polyester diol relating to the present
invention, there are enumerated aliphatic dicarboxylic acids having
a carbon number of 10-12, for example, sebasic acid, dodecanoic
diacid, and 1,11-undecane dicarboxylic acid, etc. Of those, sebasic
acid and dodecanoic diacid are preferred.
It is to be noted that within a range in which an effect by the
present invention is not deteriorated, there can be employed other
acid components, for example, aliphatic or aromatic dicarboxylic
acids such as glutaric acid, adipic acid, pimelic acid, sberic
acid, azelaic acid, terephthalic acid, isophthalic acid,
5-sulphosodium isophthalic acid, etc. These other acid components
may be even employed solely or even in mixing of two or more kinds
together with the aliphatic dicarboxylic acids having a carbon
number of 10-12. It is to be noted that the acid components for raw
materials may be even employed in the form of an ester derivative
or an acid anhydride.
Other components for constructing the polyester diol relating to
the present invention is .epsilon.-caprolactone as well as in the
present invention No. 1, and other lactones may be even employed as
auxiliary components as well as in the present invention No. 1.
As a method for the preparation of the polyester diol relating to
the present invention, there can be applied the same methods as
described in the present invention No. 1.
As content of constructing unit of the polyester diol of the
present invention, respective raw materials are employed in a range
of a proportion so that (content of constructing unit of the
polyester which is composed of a branched diol and the aliphatic
dicarboxylic acids having a carbon number of 10-12)/(content of
constructing unit of .epsilon.-caprolactone) becomes a range of
5/95-80/20 (weight ratio). Also in the case that a
poly-.epsilon.-caprolactone is employed, it is the same. In
thus-obtained polyester diol, a number average molecular weight
ranges in 500-5,000, preferably 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
A polyurethane is prepared from the polyester diol obtained as
described hereinabove and an organic diisocyanate, and a method for
the preparation of the polyurethane is the same as described in the
present invention No. 1.
As a low molecular weight diol which is a chain extender, there can
be employed a branched aliphatic diol to be employed in the present
invention or the above-described diol compounds not having branches
which can be employed together therewith. As an diamine which is a
chain extender, there can be employed the same ones as exemplified
in the present invention No. 1.
The uses of the polyurethane and descriptions relating to the
spandex filament in the present invention No. 1 can be applied to
the present invention No. 2 as it is.
Hereinafter, there are illustrated embodiments for carrying out the
present invention No. 3.
As the diols to be employed in the present invention, there is
employed 2,4-diethyl-1,5-pentane diol. However, there may be
employed at least one of other diols together with the diol, for
example, ethylene glycol, propylene glycol,
2-n-butyl-2-ethyl-1,3-propane diol, 2,2-diethyl-1,3-propane diol,
1,4-butanediol, 1,6-hexanediol, neopentyl glycol,
2-methyl-1,3-propane diol, 3-methyl-1,5-pentane diol,
1,8-nonanediol, diethylene glycol, dipropylene glycol, and
1,4-cyclohexane dimethanol, etc. In the case,
2,4-diethyl-1,5-pentane diol is employed in not less than 5% by
mol, and preferably not less than 10% by mol from a viewpoint of an
effect by the present invention, and it is preferably employed in
not more than 80% by mol, more preferably not more than 70% by mol
from an economical viewpoint.
An acid component for the polyester diol relating to the present
invention is not particularly limited, there are enumerated
aliphatic or aromatic dicarboxylic acids such as glutaric acid,
adipic acid, pimelic acid, sberic acid, azelaic acid, sebasic acid,
dodecanoic diacid, and 1,11-undecane dicarboxylic acid,
terephthalic acid, isophthalic acid, and 5-sulphosodium isophthalic
acid, etc. These acid components may be even employed solely or
even in mixing of two or more kinds. It is to be noted that the
acid components for raw materials may be even employed in the form
of an ester derivative or an acid anhydride. Of those, adipic acid
is particularly preferred.
A method for the preparation of the polyester diol relating to the
present invention is not particularly limited and, publicly-known
methods can be applied. In the reactions, catalysts are usually
employed in 0.05-1000 ppm by weight, preferably 0.1-100 ppm by
weight based on total monomers. As the catalysts, there can be
employed organic titanium compounds such as tetrabutyl titanate and
tetrapropyl titanate, tin compounds such as dibutyltin laurate, tin
octylate, dibutyltin oxide, stannous chloride, stannous bromide,
and stannous iodide. The reactions can be preferably conducted
while streaming an inert gas such as nitrogen gas from a viewpoint
of preventing discoloration of an desired product obtained.
In the polyester diol, a number average molecular weight ranges in
500-5,000, preferably 1,500-4,000. In the case of not less than
5,000, crystallinity increases in a soft segment, resulting in that
there is not apt to be obtained a spandex filament having
sufficient physical properties. The number average molecular weight
can be measured by a hydroxyl value (JIS K1557).
A polyurethane is prepared from the polyester diol obtained as
described hereinabove and an organic diisocyanate, and a method for
the preparation of the polyurethane is the same as described in the
present invention No. 1.
As a low molecular weight diol which is a chain extender, there can
be employed a diol to be employed as an essential raw material in
the present invention or the above-described diol compounds which
can be employed together therewith. As an diamine which is a chain
extender, there can be employed the same ones as exemplified in the
present invention No. 1.
The uses of the polyurethane and descriptions relating to the
spandex filament in the present invention No. 1 can be applied to
the present invention No. 3 as it is.
Hereinafter, there are illustrated embodiments for carrying out the
present invention No. 4.
The polyol (A1) having ultraviolet ray absorbable groups to be
employed in the present invention is not particularly limited and,
for example, there is enumerated a diol having two alcoholic
hydroxyl groups represented by formula (1) described below.
This is bis[3-(2H-benzotriazole-2-yl)-4-hydroxy-benzene ethanol].
As this diol, there can be employed a synthetic product and a
commercially supplied product. ##STR2##
Further, a lactone-modified polyol is not particularly limited, and
there is enumerated a diol compound represented by the formula (2).
It is to be noted that the lactone-modified polyol (A2) can be
employed solely or together with the polyol (A1) in the preparation
of a polyester polyol described hereinafter. ##STR3##
(R.sup.1 --R.sup.2 ; H, an alkyl group having a carbon number of
1-10, n and n' are an integer of 4-8, and m and m' are an integer
of 1-20)
In a method for the preparation of the ultraviolet ray absorbable
compound represented by the formula (2), lactones represented by
formula (3) described below are introduced into the diol
represented by formula (1) described hereinabove by a ring-opening
addition polymerization. ##STR4##
(R.sup.1 --R.sup.2 ; H, an alkyl group having a carbon number of
1-10, n and n' are an integer of 4-8)
As the lactones represented by the formula (3) described above,
.epsilon.-caprolactone, trimethyl-.epsilon.-caprolactone,
monomethyl-.epsilon.-caprolactone, .gamma.-butyrolactone, and
.delta.-varelolactone. Of those, .epsilon.-caprolactone is
preferred.
As the catalysts to be employed in the ring-opening addition
polymerization of the lactones represented by the formula (3)
described above to the diol represented by the formula (1)
described above, there can be employed organic titanium compounds
such as tetraethyl titanate, tetrabutyl titanate, and tetrapropyl
titanate, tin compounds such as tin octylate, dibutyltin oxide,
dibutyltin laurate, a mono-n-butyltin fatty acid salt, and a
halogenated tin compound such as stannous chloride, stannous
bromide, and stannous iodide, etc.
Use amount of the catalysts is 0.1-10000 ppm, and preferably 1-5000
ppm based on raw materials to be supplied. In the case that the use
amount of the catalysts is less than 0.1 ppm, a ring-opening
reaction is remarkably slow and it is not economical. Contrarily,
in the case that it is not less than 10000 ppm, although the
ring-opening reaction becomes quick, there become unpreferably
worse physical properties such as durability and water resistance
in a synthetic resin in which a compound obtained is employed.
Reaction temperature is 90-240.degree. C., and preferably
100-220.degree. C.
In the case that the reaction temperature is less than 90.degree.
C., the ring-opening reaction of the lactones is remarkably slow,
it is not economical. Contrarily, in the case of not less than
240.degree. C., there is caused a decomposition reaction of a
polylactone which is addition-polymerized by ring-opening.
Accordingly, the both cases are not preferred. Further, a product
having a good color hue is obtained by synthesizing in an
atmosphere of an inert gas such as nitrogen during the reaction. As
described hereinabove, an ultraviolet ray-absorbent of the present
invention is synthesized.
These details are as described in the above-described JP-A-10265557
Official Gazette.
As other polyols (A3), for example, there are enumerated ethylene
glycol, 1,2-propylene glycol, 1,3-butylene glycol,
2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol,
3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol,
dipropylene glycol, 1,4-cyclohexane dimethanol,
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, and 1,2-octyl
glycol, etc. These may be solely or even in mixing of two or more
kinds.
As the acid components in the polyester diol relating to the
present invention, adipic acid is employed and, as other acid
components, there may be also even employed the same ones as
described in the present invention No. 1 by the same
embodiments.
A method for the preparation of the polyester polyol relating to
the present invention is not particularly limited and,
publicly-known methods can be applied. In the reactions, catalysts
are usually employed in 0.05-1000 ppm (weight), preferably 0.1-100
ppm based on total monomers. As the catalysts, there can be
employed organic titanium compounds such as tetrabutyl titanate and
tetrapropyl titanate, tin compounds such as dibutyltin laurate, tin
octylate, dibutyltin oxide, stannous chloride, stannous bromide,
and stannous iodide. The reactions can be preferably conducted
while streaming an inert gas such as nitrogen gas from a viewpoint
of preventing discoloration of a desired product obtained.
In the polyester polyol, a number average molecular weight ranges
in 500-5,000, preferably 1,500-4,000. In the case of not less than
5,000, crystallinity increases in a soft segment, resulting in that
there is not apt to be obtained a spandex filament having
sufficient physical properties. The number average molecular weight
can be measured by a hydroxyl value (JIS K1557).
As content of constructing unit of the polyester polyol of the
present invention, respective raw materials are employed in a range
of a proportion so that (the content of constructing unit composed
of the polyester and adipic acid)/(content of constructing unit of
the lactone) becomes a range of 5/95-80/20 (weight ratio) A
polyurethane is prepared from the polyester diol obtained as
described hereinabove and an organic diisocyanate, and a method for
the preparation of the polyurethane is the same as described in the
present invention No. 1.
As a low molecular weight diol which is a chain extender, there can
be employed a diol to be employed as an essential raw material in
the present invention or the above-described diol compounds not
having branches which can be employed together therewith. A diamine
which is a chain extender is the same ones as exemplified in the
present invention No. 1.
The uses of the polyurethane obtained by the above-described method
can be applied to the uses described in the present invention No. 1
and, further, it is preferred to be employed as a spandex filament
in which washing resistance is particularly required.
In the present invention No. 4, as a method for giving a spandex
filament from the polyurethane, there can be applied the
descriptions in the present invention No. 1.
The spandex filament provided by the present invention is excellent
in the washing resistance as weatherability, and it is employed in
a general use form for a spandex filament, that is, a mix-knitting
and mix-weaving with a nylon and cotton, etc.
Particularly, in the case that the cotton is employed as a material
for mixing, it shows an excellent weatherability even through post
treatment steps after mix-knitting and mix-weaving, that is, a
boiling-off step, a bleaching step, and a mercerization step, etc.
in which it is treated at a high temperature under an acid or
alkali atmosphere. Further, even though it is repeatedly washed
after use as a final product, decline of the weatherability is not
almost observed.
Hereinafter, there are illustrated embodiments for carrying out the
present invention No. 5.
A high molecular-state tertiary amine compound which is appropriate
for employing in the present invention is a copolymer of a
dialkylaminoethyl(meth)acrylate. In more detail, a
dialkylaminoethyl(meth)acrylate represented by a general formula
(1) described below is employed as a comonomer.
(in the formula, R is a hydrogen or a methyl group, R.sup.0 is an
alkyl group having a carbon number of 1-4)
As a kind of specific monomers, there are employed diisopropyl
amino ethylmethacrylate (DIPAM), dimethylaminoethyl methacrylate
(DMAM), diethylaminoethyl methacrylate (DEAM), diisopropyl amino
ethylacrylate (DIPAA), dimethylaminoethyl acrylate (DMAA), and
diethylaminoethyl acrylate (DEAA), etc. Of the monomers, the DIPAM
is a most preferably employed monomer.
Use amount of the monomer ranges in usually 60% to 90% by weight,
and preferably 70% to 80% by weight in a copolymer.
On the other hand, a comonomer to be copolymerized with the
above-described dialkylaminoethyl(meth)acrylate is a reactive
monomer represented by a general formula (2) described below.
(in the formula, R is a hydrogen or a methyl group, x pieces of
R.sup.1 and R.sup.2 are independently a hydrogen atom or an alkyl
group having a carbon number of 1-12, respectively, and n pieces of
ring-opened lactone chains may be identical or different from each
other. x is an integer of 4-7, and an average value of n is
1-5)
In the case that an average value of n exceeds 5, there is caused a
problem in view of solubility to a solvent in a copolymer obtained
and compatibility with a polyurethane resin and spandex
composition.
A method for the preparation of the reactive monomer comprises
allowing to react a lactone represented by a general formula (3)
described below with a monoacrylate or methacrylate of ethylene
glycol. ##STR5##
(in the formula, x pieces of R.sup.1 and R.sup.2 are independently
a hydrogen or an alkyl group having a carbon number of 1-12,
respectively, and x is an integer of 4-7)
As the lactones represented by the formula (3), there are
enumerated .epsilon.-caprolactone,
trimethyl-.epsilon.-caprolactone,
monomethyl-.epsilon.-caprolactone, .gamma.-butyrolactone, and
.delta.-varelolactone, etc.
Preferred lactones are .epsilon.-caprolactone,
4-methyl-.epsilon.-caprolactone, 3-methyl-.epsilon.-caprolactone,
and a mixture thereof.
A more specific method for the preparation is conducted by allowing
to react the lactone with a monoacrylate or methacrylate of
ethylene glycol under the presence of approximately not more than
200 ppm, and preferably not more than 100 ppm of catalysts.
As the catalysts to be employed in the present invention, there are
enumerated one or two or more kinds of organic metal compounds and
other metal compounds, for example, tin compounds such as stannous
chloride, stannous bromide, stannous iodide, and dibutyltin oxide,
or ferric chloride, and other Levis acids and protonic acids. As
preferred catalysts, there are enumerated stannous chloride, tin
octylate, dibutyltin laurate, and other tin compounds; titanates
such as tetraisopropyl titanate, etc.
The reaction is conducted at temperatures of approximately
100-140.degree. C., and preferably approximately 110-130.degree. C.
The reaction is conducted at ordinary pressure, and may be even
conducted at a higher pressure or a lower pressure. The reaction is
conducted at an atmosphere in which oxygen concentration is
adjusted to 4% to 8%, whereby, there is preferably suppressed a
polymerization of a monoacrylate or a methacrylate of
ethyleneglycol. Reaction time of period is approximately 2-30
hours, and preferably approximately 3-20 hours.
The reaction is conducted under the presence of an appropriate
inhibitor in order to prevent a polymerization of a double bond in
a monoacrylate or a methacrylate of ethyleneglycol. As the
inhibitor, there are enumerated monomethylether of hydroquinone,
benzoquinone, phenothiazine, methyhydroquinone,
2,5-di-t-butylquinone, hydroquinone, and other free radical (a free
group) inhibitors which are publicly-known in a related field. Use
amount of the inhibitors is not more than 1000 ppm, preferably not
more than 800 ppm, and most preferably not more than 600 ppm.
In a preferred specific example, the method in the present
invention is conducted by adding a lactone to a reaction vessel
while sparging (dispersing) the lactone by an inert gas such as
nitrogen, followed by heating at reaction temperatures
(approximately 100.degree. C.-140.degree. C.). The lactone to be
employed may be dried using a common desiccating agent such as, for
example, Molecular Sieves, prior to adding to the reaction vessel.
In the case of attaining to the reaction temperature or immediately
after thereof, sparging of the inert gas is changed to an
atmospheric mixture in which oxygen concentration is adjusted to 4%
to 8%.
Various other methods may be applied. For example, a gas mixture
may be even employed only for the purpose of flushing a gas space
in the reaction vessel during through the reaction after a reaction
system is sparged by the atmospheric gas mixture in which oxygen
concentration is adjusted to 4% to 8% for a short time of period,
that is, approximately 5-10 minutes, and then, sparging is
interrupted. Otherwise, sparging of the inert gas is stopped, and
the reaction system is flushed using the mixture through the total
reaction system. And, otherwise, the gas mixture is sparged through
the system and, separately, the gas space may be even flushed
further using an inert gas. Optionally, combination of other
methods may be even conducted.
The monoacrylate or methacrylate of ethyleneglycol is mixed with
the catalysts and inhibitors, followed by adding mixture thereof to
the lactone heated. In other methods, the inhibitors may be even
added to the lactone prior to heating. Further, the lactone is
added to the heated monoacrylate or methacrylate of ethyleneglycol,
or, all reaction materials are added to the reaction vessel in an
initial stage, and the reaction may be even conducted. In a style
for adding the lactone, the monoacrylate or methacrylate,
catalysts, and inhibitors, various variations can be employed.
Final reaction mixture is maintained at the reaction temperatures
for approximately 2-30 hours.
Further, for example, the present method may be even conducted
under the presence of an appropriate solvent not containing an
active hydrogen or a polymerizable ethylenic unsaturated group. As
such the solvent, there are enumerated a ketone, an ester, an
aromatic and aliphatic hydrocarbon etc., and a mixture thereof. As
a preferred solvent, there are esters, such as cellosolve acetate,
etc.
Preferably, .epsilon.-caprolactone,
4-methyl-.epsilon.-caprolactone, 3-methyl-.epsilon.-caprolactone,
and a mixture thereof are allowed to react - with the monoacrylate
or methacrylate of ethyleneglycol in a proportion of 1 mol of the
acrylate or methacrylate with respect to 1-12 mol of the lactone.
Composition thereof may be a solid or a liquid, and most preferred
composition is a liquid.
The most preferred composition can be prepared by allowing to react
.epsilon.-caprolactone, 4-methyl-.epsilon.-caprolactone,
3-methyl-.epsilon.-caprolactone, and a mixture thereof with the
monoacrylate or methacrylate of ethyleneglycol in a proportion of 1
mol of the monoacrylate or methacrylate of ethyleneglycol with
respect to 1-5 mol of .epsilon.-caprolactone,
4-methyl-.epsilon.-caprolactone, 3-methyl-.epsilon.-caprolactone,
and a mixture thereof.
Reaction mixture is taken out, and it can be employed without
refining. Optionally, the reaction mixture can be refined by common
methods such as vacuum stripping.
As a method of the preparation of the copolymer of the present
invention, there can be applied a preparation method by a usual
radical solution polymerization as described in JP-A-02086655 by
Roden et al.
Specific detailed preparation method of the copolymer is
illustrated in Examples of the present invention.
In the copolymer of the present invention, a number average
molecular weight ranges in preferably 2000-2000000, and more
preferably 5000-500000, and a weight average molecular weight
ranges in preferably 4000-4000000, and more preferably
10000-1000000 from a viewpoint of solubility to solvents and
compatibility with a polyurethane and a spandex.
The copolymer relating to the present invention is particularly
useful in a polyurethane/spandex filament. The present invention
provides an improved polyurethane composition and spandex
composition containing a dialkylamino group-contained acrylic based
copolymer. The polyurethane composition and the spandex composition
containing additives relating to the present invention have an
excellent resistance to deterioration and discoloration, and those
show an excellent processability and permanent extension property
compared to a similar polymer containing a publicly-known high
molecular weight tertiary amine additive.
The improved spandex composition of the present invention is
prepared from a segmented polyurethane, for example, polyether, a
polyester, and a polyesterether. Such the spandex polymers are well
known and, above all, those can be prepared by the methods
disclosed in U.S. Pat. Nos. 2,929,804, 3,097,192, 3,428,711,
3,533,290, and 3,555,115. The composition of the present invention
is most useful in a spandex prepared by the polyether.
The polyurethane composition and the spandex composition relating
to the present invention are prepared by allowing to react a polyol
and/or a polyester polyol which have hydroxyl groups at both
terminals with an organic diisocyanate, and a relatively-low
molecular weight diol or diamine, etc. having two active hydrogens
which is named a chain extender and, optionally, under the presence
of catalysts.
As the polyols, for example, there are enumerated ethyleneglycol,
1,2-propylene glycol, 1,3-butylene glycol,
2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, 2-methyl-1, 3-propanediol,
3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol,
dipropylene glycol, 1,4-cyclohexane dimethanol,
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
2,4-diethyl-1,5-pentanediol, 1,2-hexaneglycol, 1,2-octylglycol, a
polyol in which there are added ethyleneoxide, propyleneoxide, and
butyleneoxide, etc. to those, and a modified product thereof, etc.
These may be solely or even in mixing of two or more kinds.
Adipic acid is employed as an acid component for the polyester diol
and, as other acid components, there may be even employed other
acid components such as aliphatic or aromatic dicarboxylic acids
such as glutaric acid, pimelic acid, sberic acid, azelaic acid,
sebasic acid, dodecanoic acid, 1,11-undecane dicarboxylic acid,
terephthalic acid, isophthalic acid, and 5-sulphosodium isophthalic
acid. The other acid components may be employed solely or even as a
mixture of two or more kinds. It is to be noted that the acid
components which are a raw material may be even employed in the
form of an ester derivative or an acid anhydride.
An organic diisocyanate is the same as described in the present
invention No. 1.
As a low molecular weight diol which is a chain extender, there can
be employed the above-described diol compounds. A diamine which is
a chain extender is the same ones as exemplified in the present
invention No. 1.
Amount of the additives which are useful for protecting the spandex
polymer of the present invention usually ranges in a wide scope
from a small amount of 0.5% by weight or so to a large amount of
10% by weight or so. Preferably, concentration of the additives
ranges in 2-6% by weight. In less than 0.5% by weight, an effect is
poor and, in largely exceeding 10% by weight, characteristics in
spandex filament unpreferably are lost.
For adding the dialkylamino(meth)acrylic-based polymer additive in
relation to the present invention to a spandex polymer, usual
methods can be applied. For example, a solution of the additive may
be prepared in the same solvent as for preparing a spandex spinning
solution. The solution can be added to the polymer solution before
molding of the polymer into a final product, for example, a
filament or a film.
Addition of the polymer in relation to the present invention is a
general style as an addition method disclosed in U.S. Pat. No.
3,428,711 by Hunt et al, and the disclosure can be referred.
In the spandex polymer composition of the present invention, other
various additives can be added for other purposes. In the other
various additives, there may be even exist a pigment or a
delustering agent, for example, titanium dioxide, an anti-blocking
agent, or a lubricant, for example, magnesium stearate and calcium
stearate, a whiteness accelerator, for example, Ultramarine Blue,
and fillers, for example, talc, etc.
Further, other than the useful uses in fibers and a film, the
polyurethane polymer containing the dialkylamino(meth)acrylate of
the present invention can be applied in, for example, uses such as
an artificial leather, etc.
Hereinafter, there are illustrated embodiments for carrying out the
present invention No. 6
As aliphatic diols to be employed in the present invention, in
addition to the branched aliphatic diols exemplified in the No. 2
of the present invention, there are enumerated the aliphatic diols
not having branches exemplified as auxiliary components in the No.
2 of the present invention. There are employed solely,
respectively, and there may be employed in mixing of two or more
kinds.
As an acid component for the polyester diol relating to the present
invention, there are enumerated aliphatic dicarboxylic acids having
a carbon number of 9-12, for example, azelaic acid, sebasic acid,
dodecanoic diacid, and 1,11-undecane dicarboxylic acid, etc. Of
those, azelaic acid, sebasic acid, and dodecanoic diacid are
preferred.
It is to be noted that within a range in which an effect by the
present invention is not deteriorated, there can be employed other
acid components, for example, aliphatic or aromatic dicarboxylic
acids such as glutaric acid, adipic acid, pimelic acid, sberic
acid, terephthalic acid, isophthalic acid, and 5-sulphosodium
isophthalic acid, etc. These other acid components may be even
employed solely or even in mixing of two or more kinds together
with the aliphatic dicarboxylic acids having a carbon number of
9-12. It is to be noted that the acid components for raw materials
may be even employed in the form of an ester derivative or an acid
anhydride.
Other component which constructs the polyester diol in relation to
the present invention is .epsilon.-caprolactone, and other lactones
may be employed as auxiliary components as well as in the No. 1 of
the present invention.
As a method for the preparation of the polyester diol in the
present invention, the same method can be applied as described in
the No. 1 of the present invention.
As content of constructing unit of the polyester diol of the
present invention, respective raw materials are employed in a range
of a proportion so that (content of constructing unit of the
polyester composed of an aliphatic diol and adipic acid)/(content
of constructing unit of .epsilon.-caprolactone) becomes a range of
5/95-80/20 (weight ratio). Also in the case that a
poly-.epsilon.-caprolactone is employed, it is the same. In
thus-obtained polyester diol, a number average molecular weight
ranges in 500-5,000, preferably. 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
A polyurethane is prepared from the polyester diol obtained as
described hereinabove and an organic diisocyanate, as described in
the present invention No. 1.
As the above-described low molecular weight diol which is a chain
extender, there can be employed the branched aliphatic diols to be
employed in the present invention or the diol compounds which can
be employed together therewith. As an diamine which is a chain
extender, there can be employed the same ones as exemplified in the
present invention No. 1.
The polyurethane obtained by the above-described methods is
employed in a variety of uses in which a usual polyurethane is
employed, for example, a thermoplastic elastomer, a hard or soft.
urethane foam, an adhesive, an artificial leather, and coating,
etc., and particularly, it is preferred to employ for a spandex
filament.
It is to be noted that the polyurethane to be employed for the
artificial leather in the present invention can be employed in a
mode of any one of a solvent-based urethane or water-based urethane
and, hereinafter, both will be illustrated.
In the solvent-based urethane to be employed in the present
invention, modulus in 100% extension preferably ranges in 15-150
kg/cm.sup.2, and preferably 15-70 kg/cm.sup.2. In the case that the
modulus in 100% extension is less than 15 kg/cm.sup.2, durability
occasionally becomes worse in a sheet obtained and, it becomes
difficult to industrially produce because of a large longitudinal
extension in a step for extracting-removing components of a matrix
region.
Further, in the case that the modulus in 100% extension is more
than 150 kg/cm.sup.2, there cannot be obtained an artificial
leather having a high density, a low repellent property, and
excellent feeling at which the present invention aims.
Since the polyurethane to be employed in the present invention is
impregnated into a cloth, it is employed as a solution. As a
preferred solvent in the case, there are enumerated dimethyl
formamide, dimethyl acetoamide, dioxane, and tetrahydrofran,
etc.
In the present invention, an impregnated polyurethane is coagulated
by a nonsolvent, and it requires to apply a so-called wet
coagulation method. There is not preferred a method in which a
solvent is removed by impregnation and drying without coagulating
by a nonsolvent, that is, since feeling becomes very hard in a
dry-coagulation method and a low repellent feeling is not obtained,
it is not preferred. As a liquid in a bath for wet-coagulating a
polyurethane, there are typically enumerated water and a mixed
solution of water with the above-described solvents. Further, as a
solvent to be employed for extracting matrix components of a fine
fibers-producible type fiber, there are enumerated aromatic
hydrocarbons such as benzene, toluene, and xylene, halogenated
hydrocarbons such as trichloroethylene, tetrachloroethylene, and
carbon tetrachloride, etc.
In the polyurethane to be employed in the present invention, there
can be added a variety of additives such as, for example, a
phosphorous-based compound and a halogen-contained compound which
are a flame retardant, an antioxidant, an ultraviolet ray
absorbent, pigments, dyes, and plasticizers, etc. However, an
effect is not shown even though there are added substances
simultaneously extracted in a step for extracting a matrix resin
component.
Cloth to be employed in the present invention is not particularly
limited, and nonwoven cloth and woven cloth can be employed. Of
those, there is preferred a nonwoven cloth three-dimensionally
entangled. Fibers or filaments constructing the clothes are a fine
fibers or filament-producible type fiber or filament having a
matrix-domain structure in which a thermoplastic resin which can be
extracted and removed by a solvent is a matrix resin components and
a fiber-formable thermoplastic resin is a domain component. As the
thermoplastic resin which is employed as the domain component,
there are enumerated, for example, a polyamide resin and a
polyester resin, and as the thermoplastic resin which is employed
as the matrix component which can be extracted by a solvent, there
are enumerated, for example, a polyolefine, a polystyrene, a
modified polyvinyl alcohol-based resin, and a water-soluble
polyester resin, etc.
In more detail, as a specific example of the domain component resin
for employing in the present invention, there are enumerated
6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, a spinnable polyamide
having an aromatic group, polyethylene terephthalate, polybutylene
terephthalate, sulphoisophthalic acid-based polyethylene
terephthalate, and sulphoisohpthalic-based polybutylene
terephthalate, etc. On the other hand, as a polymer constructing
the matrix component resin, there is enumerated a resin which has a
different solubility to a solvent from the domain component resin,
and which has only a small affinity to the domain component resin
and, moreover, which has a smaller melt viscosity than that in the
domain component resin under spinning conditions. For example,
there are enumerated a polyethylene, a polypropylene, an
ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer,
an ethylene-acrylate copolymer, an ethylene-.alpha.-olefine
copolymer, a polystyrene, a hydrogenated product of a
styrene-isoprene copolymer, a styrene-butadiene copolymer, a
hydrogenated product of a styrene-butadiene copolymer, a modified
polyvinyl alcohol, and a modified polyester, etc.
As a method for the preparation of fibers composed of the matrix
component resin and the domain component resin, there are
enumerated a method in which a spinning is conducted by forming a
mixed system while dissolving in an identical dissolving system
after mixing the matrix component resin and the domain component
resin in a fixed proportion, a method in which a spinning is
conducted by dissolving in an independent system, respectively, and
by forming a mixed system through repeating a combining-separating
of both polymer streams at a head portion of a spinning machine in
plural times, and a method in which a spinning is conducted by
dissolving in an independent dissolving system, respectively, and
by combining both polymer streams each other through regulating a
fiber shape at a head portion of a spinning machine. Proportion
occupied by the the domain component resin in the fibers is
preferably 40-80% by weight, and pieces of very fine fibers in the
cross-section of fibers are not less than 5, particularly, those
preferably range in 5-10000 pieces. Thus-spun very fine
fiber-producible type fibers are optionally through a usual
treatment step for fibers such as an extension step and
heat-setting step to prepare fibers having size of 2-15 deniers, an
average size of not more than 0.2 denier in the very fine fibers,
and preferably not more than 0.1 denier and not less than 0.001
denier.
Thus-spun very fine fiber-producible type fibers are bloomed
through a blooming machine, followed by forming random web or cross
wrap through a weaver and by piling a fiber web obtained in order
to give a desired weight and thickness. Subsequently, the fiber web
is treated for entangling through conventionally publicly-known
methods such as needle punching, water jetting, and air jetting to
prepare a nonwoven cloth in which fibers are entangled. Of course,
a textile may be even formed after preparing spun fibers or
multi-filaments from the very fine fiber-producible type fibers by
conventional methods. Further, the nonwoven cloth may be even piled
with the textiles.
In fibrous base materials, a density of 0.2-0.5 g/cm.sup.3 is
preferred before impregnating a polyurethane in order to obtain an
excellent filled up-touch and a good feeling and, more preferably,
it ranges in 0.25-0.40 g/cm.sup.3. In the fibrous base materials,
when the density is less than 0.2 g/cm.sup.3, surface flatness
becomes worse in a sheet obtained. Further, in the case of being
more than 0.5 g/cm.sup.3, there are not occasionally obtained an
excellent filled up-touch and a good feeling which are a purpose in
the present invention by high-densification in a sheet
obtained.
The sheet which is an artificial leather in relation to the present
invention is comprised a cloth which is a textile of very fine
fibers and a polyurethane existing in inside clearance of fibers,
and the polyurethane exists between a very fine fiber bundle and a
very fine fiber bundle and, it is preferred that it does not exist
in inside of the very fine fiber bundle. In the case that the
polyurethane does not substantially exist in inside of the very
fine fiber bundle, very fine fibers are not fixed by the
polyurethane, whereby, a sheet obtained is rich in the filled
up-touch and, moreover, the fibers in the sheet obtained are
sufficiently released from the polyurethane, whereby, there is
obtained a rubber-like soft feeling not having a repellent
feeling.
In the sheet of the present invention, ratio of the polyurethane in
the sheet preferably ranges in 15-60% by weight, and preferably
25-50% by weight. In the case that the ratio of the polyurethane is
less than 15% by weight, physical properties such as surface
strength occasionally become large with a lapse of time, or feeling
by hands occasionally becomes bulky and paper-like. In the case
that the ratio of the polyurethane is higher than 60% by weight,
surface flatness occasionally becomes worse in the sheet obtained,
or feeling occasionally becomes hard.
By forming a surface layer through coating a resin with spraying or
gravure, etc. onto a polyurethane-impregnated cloth obtained by the
above methods, or, by a method in which a cloth is unified with a
resin layer formed on a releasing paper, there can be obtained an
artificial leather-like sheet having a silver-colored surface.
Further, a suede-like sheet can be also obtained by conducting
buffing the surface of the polyurethane-impregnated cloth using a
sandpaper, etc.
On the other hand, in the case that the polyurethane emulsion
prepared by using a specified polyester diol in the present
invention is applied to the artificial leather, hydrolysis
resistance is improved compared to an artificial leather obtained
by impregnating a polyurethane emulsion prepared using a polyester
polyol obtained by condensation reaction of a dibasic acid with
glycols, and it is excellent in hydrolysis resistance and heat
resistance even though being compared to an artificial leather
obtained by impregnating a polyurethane emulsion prepared using a
polyether polyol such as polyalkylene glycols or alkylene
oxide-adducts. Further, in the case of an artificial leather in
which a polyurethane emulsion is impregnated which is prepared by
using a specified polyester diol in the present invention, a soft
feeling is obtained. As described hereinabove, in a word, there is
obtained a very excellent artificial leather having many satisfied
physical properties by using a specified polyester diol in the
present invention.
EXAMPLES
Hereinafter, although the present inventions No. 1 to No. 5 are
specifically illustrated by Examples, the present invention is not
limited thereto. It is to be noted that "part" in the Examples and
Comparative Examples is "part by weight", so far as not being
particularly noticed.
Hereinafter, the present invention No. 1 is specifically
illustrated by Examples.
In the Examples and Comparative Examples, compounds employed are
named by abbreviations. Table 1-1 shows relationship between the
abbreviations and the compounds. Further, there were measured
retention ratio of strength, 200%-modulus, and retention ratio of
200%-modulus by the following methods.
(1) Retention ratio of strength: {stress in fracture after an
alkali treatment (in the Table, "strength after treatment")/stress
in fracture (in the Table, "strength")}.times.100%
(2) 200%-modulus: Stress in 200% extension
(3) Retention ratio of 200%-modulus: (200%-modulus after an alkali
treatment/200%-modulus).times.100
TABLE 1-1 Abbreviated word Compound BEPD
2-n-butyl-2-ethyl-1,3-propanediol DEPD 2,2-diethyl-1,3-propanediol
DEND 2,4-diethyl-1,5-propanediol AA adipic acid CL
.epsilon.-caprolactone NPG neopentylglycol BD 1,4-butanediol HD
1,6-hexanediol MPD 3-methyl-1,5-pentanediol
It is to be noted that evaluation of hydrolysis resistance in
alkali in relation to a polyurethane elastic fiber obtained was
conducted under an alkali atmosphere as shown below.
(Hydrolysis Resistance in Alkali in Relation to a Polyurethane
Elastic Fiber)
Polyurethane elastic fiber was immersed in 60 g/liter aqueous
solution of sodium hydroxide at 98.degree. C. while maintaining a
constant length, and the polyurethane elastic fiber was evaluated
by retention ratio of strength and retention ratio of
200%-modulus.
Examples 1-1 to 1-10
There were fed 101 parts a polyester polyol thermally-melted at
80.degree. C. having an average molecular weight of 2000 which has
a composition shown in Table 1-2, 39 parts of MDI
(4,4'-diphenylmethane diisocyanate) thermally-melted at 45.degree.
C., and 9.5 parts of BD into a twin-screw extruder using a volume
displacement pump to conduct a continuous melt-polymerization at
240.degree. C. A polyurethane prepared was extruded into water in a
strand state to pelletize by cutting. Pellets were dried at
80.degree. C. for 24 hours under a nitrogen stream.
The pellets were spun at a spinning temperature of 217.degree. C.
and spinning speed of 600 m/minute by a spinning machine which is a
single-screw extruder to obtain an elastic monofilament of the
polyurethane having 40 deniers.
Using the elastic monofilament of the polyurethane, various
physical properties and hydrolysis resistance in alkali were
evaluated. Results are shown in Table 1-3. In all cases, it is
excellent in physical properties as fibers and hydrolysis
resistance in alkali.
Comparative Examples 1-1 to 1-7
Using polyester polyols as shown in Table 1-3, a polyurethane
elastic fiber was obtained by the same procedures as in the
Examples. The polyester polyols have (a constructing unit content
of a polyester composed of at least one kind selected from the
group of 2-n-butyl-2-ethyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, and 2,4-diethyl-1, 5-pentanediol)/(a
constructing unit content of .epsilon.-caprolactone) of an outside
range of 5/95-80/20 (weight ratio). Physical properties and
hydrolysis resistance in alkali were evaluated. Results are shown
in Table 1-3.
TABLE 1-2 Component ratio of Diol (%) PE (wt %) CL (wt %) BEPD DEPD
DEND NPG ED BD HD Diol/AA CL Example 1-1 100 40 60 Example 1-2 100
40 60 Example 1-3 100 40 60 Example 1-4 100 20 80 Example 1-5 100
60 40 Example 1-6 100 80 20 Example 1-7 50 50 40 60 Example 1-8 50
50 40 60 Example 1-9 50 50 40 60 Example 1-10 50 50 40 60 C. Exam.
1-1 30 70 100 0 C. Exam. 1-2 50 50 100 0 C. Exam. 1-3 100 40 60 C.
Exam. 1-4 100 100 0 C. Exam. 1-5 100 100 0 C. Exam. 1-6 0 100 C.
Exam. 1-7 100 95 5 In the Table 1-2, C. Exam. means Comparative
Example.
In the Table, PE (wt %) means the weight proportion of the
constructing unit content of a polyester composed obtained from a
various diols and dicarboxylic acids, and CL means the constructing
unit content of .epsilon.-caprolactone.
TABLE 1-3 200% Alkali Strength Extension modulus Strength A.T Rete.
Ratio 200% modulus Ret. Ratio (g/d) (%) (g/d) (g/d) (%) (g/d) (%)
Example 1-1 1.56 510 0.36 1.45 93 0.33 92 Example 1-2 1.54 514 0.36
1.46 95 0.34 94 Example 1-3 1.58 518 0.36 1.50 95 0.34 94 Example
1-4 1.65 504 0.39 1.35 82 0.32 82 Example 1-5 1.50 528 0.34 1.38 92
0.31 90 Example 1-6 1.40 547 0.32 1.37 98 0.31 96 Example 1-7 1.41
513 0.33 1.27 90 0.29 89 Example 1-8 1.48 521 0.32 1.30 88 0.28 86
Example 1-9 1.52 524 0.34 1.35 89 0.29 86 Example 1-10 1.58 512
0.36 1.45 92 0.32 88 C. Exam. 1-1 1.28 460 0.32 1.10 86 0.26 82 C.
Exam. 1-2 1.19 512 0.28 0.98 82 0.23 82 C. Exam. 1-3 1.52 518 0.35
0.99 65 0.22 63 C. Exam. 1-4 0.75 320 0.12 0.56 75 0.09 72 C. Exam.
1-5 1.76 405 0.44 0.97 55 0.23 53 C. Exam. 1-6 1.79 402 0.47 0.98
55 0.25 53 C. Exam. 1-7 1.29 458 0.33 1.10 85 0.27 81 In the Table
1-3, abbreviations are as follows. C. Exam.: Comparative Example
Strength A.T: Strength after treatment Rete. Ratio: Retention
Ratio
As clearly shown in the Table 1-3, it is confirmed that the
polyurethane elastic fibers in the Examples 1-1 to 1-10 do not show
a remarkable decline of strength and modulus in 200%-extension
after hydrolysis in alkali compared to those of the Comparative
Examples, and have a satisfied physical properties as fibers. The
polyurethane elastic fibers in the Examples 1-1 to 1-10 have (a
constructing unit content of a polyester composed of at least one
kind selected from the group of 2-n-butyl-2-ethyl-1, 3-propanediol,
2,2-diethyl-1,3-propanediol, and2,4-diethyl-1,5-pentanediol)/(a
constructing unit content of .epsilon.-caprolactone) of 5/95-80/20
(weight ratio).
Hereinafter, the present invention No. 2 is specifically
illustrated by Examples.
In the Examples and Comparative Examples, compounds employed are
named by abbreviations. Table 2-1 shows a relationship between the
abbreviations and the compounds. Measurement methods for retention
ratio of strength, 200%-modulus, and retention ratio of
200%-modulus are the same as in the present inventions No. 1.
TABLE 2-1 Abbreviated word Compound BEPD
2-n-butyl-2-ethyl-1,3-propanediol MPD 3-methyl-1,5-pentanediol DEND
2,4-diethyl-1,5-propanediol AA adipic acid DA sebasic acid DDA
dodecanoic diacid CL .epsilon.-caprolactone BD 1,4-butanediol HD
1,6-hexanediol
It is to be noted that evaluations for hydrolysis resistance in
alkali of a polyurethane elastic fiber obtained were likewise
conducted as in the present inventions No. 1.
Examples 2-1 to 2-10
There were fed 101 parts a polyester polyol thermally-melted at
80.degree. C. having an average molecular weight of 2000 which has
a composition shown in Table 2-2, 39 parts of MDI
(4,4'-diphenylmethane diisocyanate) thermally-melted at 45.degree.
C., and 9.5 parts of BD into a twin-screw extruder using a volume
displacement pump to conduct a continuous melt-polymerization at
240.degree. C. A polyurethane prepared was extruded into water in a
strand state to pelletize by cutting. Pellets were dried at
80.degree. C. for 24 hours under a nitrogen stream.
The pellets were spun at a spinning temperature of 217.degree. C.
and spinning speed of 600 m/minute by a spinning machine which is a
single-screw extruder to obtain an elastic monofilament of the
polyurethane having 40 denier.
Using the elastic monofilament of the polyurethane, various
physical properties and hydrolysis resistance in alkali were
evaluated. Results are shown in Table 2-3. In all cases, it is
excellent in physical properties as fibers and hydrolysis
resistance in alkali.
Comparative Examples 2-1 to 2-7
Using polyester polyols as shown in Table 2-2, a polyurethane
elastic fiber was obtained by the same procedures as in the
Examples. The polyester polyols have (a constructing unit content
of a polyester composed of a branched diol and an aliphatic
dicarboxylic acid having a carbon number of 10-12)/(a constructing
unit content of .epsilon.-caprolactone) of an outside range of
5/95-80/20 (weight ratio). Physical properties and hydrolysis
resistance in alkali were evaluated. Results are shown in Table
2-3.
TABLE 2-2 Component ratio of Diol (%) PE (wt %) CL (wt %) BEPD MPD
DEND BD HD Acid Diol/Acid CL Example 2-1 100 DA 40 60 Example 2-2
100 DA 40 60 Example 2-3 100 DA 40 60 Example 2-4 100 DA 20 80
Example 2-5 100 DA 60 40 Example 2-6 100 DA 80 20 Example 2-7 100
DDA 40 60 Example 2-8 50 50 DA 40 60 Example 2-9 50 50 DA 40 60
Example 2-10 50 50 DDA 40 60 C. Exam. 2-1 30 70 AA 100 0 C. Exam.
2-2 50 50 AA 100 0 C. Exam. 2-3 100 100 AA 40 60 C. Exam. 2-4 100
AA 100 0 C. Exam. 2-5 100 AA 100 0 C. Exam. 2-6 AA 0 100 C. Exam.
2-7 100 AA 95 5 In the Table 2-2, C. Exam. means Comparative
Example.
In the Table, PE (weight %) means the weight proportion of the
constructing unit content of a polyester composed obtained from a
various diols and dicarboxylic acids, and CL means the constructing
unit content of .epsilon.-caprolactone.
TABLE 2-3 200% Alkali Strength Extension modulus Strength A.T Rete.
Ratio 200% modulus Ret. Ratio (g/d) (%) (g/d) (g/d) (%) (g/d) (%)
Example 2-1 1.55 508 0.36 1.43 92 0.33 91 Example 2-2 1.52 513 0.36
1.41 93 0.33 92 Example 2-3 1.51 516 0.36 1.40 93 0.33 92 Example
2-4 1.61 502 0.39 1.43 89 0.34 87 Example 2-5 1.48 519 0.34 1.35 91
0.30 89 Example 2-6 1.42 526 0.32 1.32 93 0.30 93 Example 2-7 1.48
527 0.33 1.36 92 0.30 91 Example 2-8 1.42 530 0.32 1.26 89 0.28 88
Example 2-9 1.52 516 0.34 1.32 87 0.30 88 Example 2-10 1.48 508
0.36 1.35 91 0.31 85 C. Exam. 2-1 1.28 460 0.32 1.10 86 0.26 82 C.
Exam. 2-2 1.19 512 0.28 0.98 82 0.23 82 C. Exam. 2-3 1.52 518 0.35
0.99 65 0.22 63 C. Exam. 2-4 0.75 320 0.12 0.56 75 0.09 72 C. Exam.
2-5 1.76 405 0.44 0.97 55 0.23 53 C. Exam. 2-6 1.79 402 0.47 0.98
55 0.25 53 C. Exam. 2-7 1.29 458 0.33 1.10 85 0.27 81 In the Table
2-3, abbreviations are as follows. C. Exam.: Comparative Example
Strength A.T: Strength after treatment Rete. Ratio: Retention
Ratio
As clearly shown in the Table 2-3, it is confirmed that the
polyurethane elastic fibers in the Examples 2-1 to 2-10 do not show
a remarkable decline of strength and modulus in 200%-extension
after hydrolysis in alkali compared to those of the Comparative
Examples, and have a satisfied physical properties as fibers. The
polyurethane elastic fibers in the Examples 2-1 to 2-10 have (a
constructing unit content of a polyester composed of the branched
diols and dicarboxylic acids having a carbon number of 10-12)/(a
constructing unit content of .epsilon.-caprolactone) of 5/95-80/20
(weight ratio).
Hereinafter, the present invention No. 3 is specifically
illustrated by Examples.
In the Examples and Comparative Examples, compounds employed are
named by abbreviations. Table 3-1 shows a relationship between the
abbreviations and the compounds. Measurement methods for retention
ratio of strength, 200%-modulus, and retention ratio of
200%-modulus are the same as in the present inventions No. 1.
TABLE 3-1 Abbreviated word Compound BEPD
2-n-butyl-2-ethyl-1,3-propanediol DEPD 2,2-diethyl-1,3-propanediol
DEND 2,4-diethyl-1,5-pentanediol AA adipic acid CL
.epsilon.-caprolactone NPG neopentylglycol BD 1,4-butanediol HD
1,6-hexanediol MPD 3-methyl-1,5-pentanediol
It is to be noted that evaluations for hydrolysis resistance in
alkali of a polyurethane elastic fiber obtained were likewise
conducted as in the present inventions No. 1.
Examples 3-1 to 3-7
There were fed 101 parts of a polyester polyol thermally-melted at
80.degree. C. having an average molecular weight of 2000 which has
a composition shown in Table 3-2, 39 parts of MDI
(4,4'-diphenylmethane diisocyanate) thermally-melted at 45.degree.
C., and 9.5 parts of BD into a twin-screw extruder using a volume
displacement pump to conduct a continuous melt-polymerization at
240.degree. C. A polyurethane prepared was extruded into water in a
strand state to pelletize by cutting. Pellets were dried at
80.degree. C. for 24 hours under a nitrogen stream.
The pellets were spun at a spinning temperature of 217.degree. C.
and spinning speed of 600 m/minute by a spinning machine which is a
single-screw extruder to obtain an elastic monofilament of the
polyurethane having 40 denier.
Using the elastic monofilament of the polyurethane, various
physical properties and hydrolysis resistance in alkali were
evaluated. Results are shown in Table 3-3. In all cases, it is
excellent in physical properties as fibers and hydrolysis
resistance in alkali.
Comparative Examples 3-1 to 3-7
Using polyester polyols as shown in Table 3-2, a polyurethane
elastic fiber was obtained by the same procedures as in the
Examples. The polyester polyols do not contain
2,4-diethyl-1,5-pentanediol. Physical properties and hydrolysis
resistance in alkali were evaluated. Results are shown in Table
3-3.
TABLE 3-2 Component ratio of Diol (%) BEPD DEPD DEND NPG ED BD HD
Example 3-1 10 90 Example 3-2 30 70 Example 3-3 50 50 Example 3-4
70 30 Example 3-5 30 40 30 Example 3-6 30 40 30 Example 3-7 50 30
40 30 C. Exam. 3-1 30 70 C. Exam. 3-2 50 50 C. Exam. 3-3 100 C.
Exam. 3-4 100 C. Exam. 3-5 100 C. Exam. 3-6 100 C. Exam. 3-7 100 In
the Table 3-2, C. Exam. means Comparative Example.
TABLE 3-3 200% Alkali Strength Extension modulus Strength A.T Ret.
Ratio 200% modulus Ret. Ratio (g/d) (%) (g/d) (g/d) (%) (g/d) (%)
Example 3-1 1.65 504 0.39 1.35 82 0.32 82 Example 3-2 1.50 528 0.34
1.38 92 0.31 90 Example 3-3 1.40 547 0.32 1.37 98 0.31 96 Example
3-4 1.41 513 0.33 1.27 90 0.29 89 Example 3-5 1.56 510 0.36 1.45 93
0.33 92 Example 3-6 1.54 514 0.36 1.46 95 0.34 94 Example 3-7 1.58
518 0.36 1.50 96 0.34 94 C. Exam. 3-1 1.28 460 0.32 1.10 86 0.26 82
C. Exam. 3-2 1.19 512 0.28 0.98 82 0.23 82 C. Exam. 3-3 1.52 518
0.35 0.99 65 0.22 63 C. Exam. 3-4 0.75 320 0.12 0.56 75 0.09 72 C.
Exam. 3-5 1.76 405 0.44 0.97 55 0.23 53 C. Exam. 3-6 1.79 402 0.47
0.98 55 0.25 53 C. Exam. 3-7 1.29 468 0.33 1.10 85 0.27 81 In the
Table 3-3, abbreviations are as follows. C. Exam.: Comparative
Example Strength A.T: Strength after treatment Rete. Ratio:
Retention Ratio
As clearly shown in the Table 3-3, it is confirmed that the
polyurethane elastic fibers in the Examples 3-1 to 3-7 do not show
a remarkable decline of strength and modulus in 200%-extension
after hydrolysis in alkali compared to those of the Comparative
Examples, and have a satisfied physical properties as fibers. The
polyurethane elastic fibers in the Examples 3-1 to 3-7 have a
polyester diol containing 10-70% of a specified diol by mol based
on diol components constructing the polyester diol.
Hereinafter, the present invention No. 4 is specifically
illustrated by Examples.
Synthesis Example 4-1
A glass-made flask equipped with a condenser, a tube for supplying
nitrogen, a thermometer, and an agitator was charged with 129.3 g
of bis[3-(2H-benzotriazole-2-yl)4-hydroxy-benzene ethanol]methane
(a trade name of "MBEP" manufactured by Otsuka Kagaku, Ltd.), 170.3
g of .epsilon.-caprolactone, and 50 ppm of mono-n-butyltin
aliphatic acid salt (a trade name of "SCAT-24" manufactured by
Sankyo Yuki Gosei, Ltd.). After having maintained a reaction
temperature at 150.degree. C. for 6 hours, concentration of
.epsilon.-caprolactone in a reaction liquid was measured by a
gas-chromatograph, and the reaction was terminated at the
concentration of 0.43%. Reaction product was a liquid-state
substance at room temperatures having an acid value (mgKOH/g) of
1.8, a viscosity of 2645 CP/60.degree. C., a number average
molecular weight (MN) by GPC of 1391, a weight average molecular
weight (MW) by GPC of 1688, and MW/MN=1.213.
Synthesis Example 4-2
The same apparatus as in the Synthesis Example 4-1 was charged with
93.7 g of bis[3-(2H-benzotriazole-2-yl)4-hydroxy-benzene
ethanol]methane (a trade name of "MBEP" manufactured by Otsuka
Kagaku, Ltd.), 206.3 g of .epsilon.-caprolactone, and 50 ppm of
mono-n-butyltin aliphatic acid salt (a trade name of "SCAT-24"
manufactured by Sankyo Yuki Gosei, Ltd.). After having maintained a
reaction temperature at 150.degree. C. for 6 hours, concentration
of .epsilon.-caprolactone in a reaction liquid was measured by a
gas-chromatograph, and the reaction was terminated at the
concentration of 0.55%. Reaction product was a substance which is a
solid at room temperature having an acid value (mgKOH/g) of 2.5, a
viscosity of 987 CP/60.degree. C., MN of 2017, MW of 2465, and
MW/MN=1.222.
Example 4-1
Polyester polyols were prepared from an
.epsilon.-caprolactone-modified polyol obtained in the Synthesis
Example 4-1 and Synthesis Example 4-2 and adipic acid, or MBEP
employed in the Synthesis Examples and adipic acid, respectively.
The polyester polyols and thermally-melted MDI
(4,4'-diphenylmethane diisocyanate), and BD (1,4-butanediol) were
fed into a twin-screw extruder using a volume displacement pump to
conduct a continuous melt-polymerization at 240.degree. C. A
polyurethane prepared was extruded into water in a strand state to
pelletize by cutting. Pellets were dried at 80.degree. C. for 24
hours under a nitrogen stream. The pellets were spun at a spinning
temperature of 217.degree. C. and spinning speed of 600 m/minute by
a spinning machine which is a single-screw extruder to obtain a 40
denier elastic monofilament of the polyurethane. Since the elastic
monofilament of the polyurethane has an ultraviolet ray absorbable
group in the molecule, it is more excellent in weatherability and
washing resistance compared to a spandex filament in which an
ultraviolet ray absorbent is added.
Hereinafter, the present invention No. 5 is specifically
illustrated by Examples.
<Experimental Method>
Various properties and parameters of copolymers in the present
invention were measured as follows.
(1) Evaluation of solubility to solvents
As being shown in Examples 5-1 to 5-6 and Comparative Examples 5-1
to 5-2, a polymer solution was prepared, and outer appearance when
cooled to room temperature (25.degree. C.) was observed. Evaluation
is as follows, when the solution is opaque, it is worse, and when
it is transparent, it is good.
(2) Preparation of an experimental sample
In order to evaluate an applicability as an additive for a spandex
polymer, a polymer film sample was prepared which contains an
additive.
In the preparation of the film sample, a polymer solution was
prepared, substantially, according to a method described in the
Example 5-1. Subsequently, the polymer solution was completely
mixed with 20 g of an N,N-dimethylacetamide solvent containing a
desired amount of an experimental additive. Subsequently, the
polymer solution containing the additive was stood for 30
minutes.
Subsequently, a film was cast on "Mylar (Mylar)" which is a
polyester sheet using a doctor knife device having a broad gap of
0.51 cm.
N,N-dimethylacetamide solution was cast to obtain an experimental
sample having a dimension of approximately 20.3 cm.times.8.9 cm.
The film cast was dried in air for 24 hours, and the experimental
sample was stripped from the "Mylar" sheet.
After preparation of the experimental sample, the sample was
immersed in a water bath. In order to suppose a water bath for
washing, the sample was immersed in a bath having 2 liters of water
containing 8 g of "Duponol (Duponol)" which is an anion surface
active agent (diethanolamine laurylsulphate manufactured by E.I.
Dupon't, Ltd.), 5 g of sodium tetrapirorate, and 1.5 g of
ethylenediamine tetracetate for 1 hour. After having taken out the
sample, and even a trace amount of the additives in the bath was
repeatedly washed and removed using a pure water until becoming not
detected in water.
Example 5-1
<Preparation of a copolymer (copolymer 1) of a dialkyl
aminoethyl(meth)acrylate with a monomethacrylate of
.epsilon.-caprolactone-modified ethyleneglycol>
Using a 300 cc 4-necked flask equipped with an agitator, a
thermometer, a dropping funnel, and a device for supplying
nitrogen, first of all, the flask was sufficiently purged by
nitrogen, and 25 g of dimethylacetamide (DMAc) was added, followed
by heating to 85.degree. C. so that temperature in the flask
becomes constant. Subsequently, various components having the
weight described below were dropped into the flask at a constant
speed over 4 hours.
2,2-azobis-2-methylbutyronitrile (ABN-E): 0.675 g
Diisopropyl aminoethylmethacrylate (DIPAM): 45 g
Placcel FM2D (an .epsilon.-caprolactone-adduct of ethyleneglycol
monomethacrylate: manufactured by Daicel Chemical Industries,
Ltd.): 15 g
Dimethylacetamide (DMAc): 15.4 g
Dropping reaction was terminated after 4 hours, subsequently, an
aging reaction was conducted at 85.degree. C. for 1 hour, followed
by adding 0.675 g of ABN-E into the flask. After that, a reaction
was conducted at temperature of 85.degree. C. for 3 hours. Solid
components concentration (N.V.) was 57.1%, and a molecular weight
of a polymer was measured by a gel permeation chromatographic (GPC)
method, and the following results were obtained.
It is to be noted that in order to evaluate a solubility to DMAc,
an outer appearance was observed at room temperature (25.degree.
C.).
A solution obtained was transparent, and it was confirmed that the
solubility is excellent.
Number average molecular weight Mn: 13700
Weight average molecular weight Mw: 46100
Molecular weight distribution Mw/Mn: 3.36
Examples 5-2 to 5-6
<Preparation of copolymers (copolymers 2-6) of a dialkyl
aminoethyl(meth)acrylate with a monomethacrylate of
.epsilon.-caprolactone-modified ethyleneglycol>
The same procedures as in the Example 5-1 were likewise conducted
except that a solution having composition shown in Table 5-1 was
added dropwise to obtain copolymers 2-6. Table 5-1 collectively
shows results (incapability of measuring means incapability of
detecting because of a close refraction index to a solvent) of a
solid concentration, a GPC analysis, and a solubility to DMAc.
Comparative Examples 5-1 to 5-2
<Preparation of dialkyl aminoethyl(meth)acrylate-based
copolymers (comparative copolymers 1-2) not having a
monomethacrylate of .epsilon.-caprolactone-modified ethyleneglycol
as a constructing component>
The same procedures as in the Example 5-1 were likewise conducted
except that a solution having composition shown in Table 5-1 was
added dropwise to obtain copolymers 1 and 2. Table 5-1 collectively
shows results (incapability of measuring means incapability of
detecting because of a close refraction index to a solvent) of a
solid components concentration, a GPC analysis, and a solubility to
DMAc.
Examples 5-7 to 5-12 and Comparative Examples 5-3 to 5-4
<Evaluation of heat set efficiency in a spandex film containing
an additive which is a copolymer (copolymers 2 to 6) of a dialkyl
aminoethyl(meth)acrylate with a monomethacrylate of
.epsilon.-caprolactone-modified ethyleneglycol>
An N,N-dimethylacetamide solution of a segmented polyurethane was
prepared according to a general method (for example, first
descriptions in Example 11 and descriptions in Example I) described
in U.S. Pat. No. 3,428,711
A mixture was prepared by completely mixing p,p'-methylenediphenyl
diisocyanate and polytetramethylene glycol (a molecular weight of
approximately 1800) in a molar ratio of 1.63, followed by preparing
an isocyanate-terminatedpolyether (that is, a terminal-treated
glycol having an NCO content of 2.40%) while maintaining
temperature at approximately 80-90.degree. C. for 90-100 minutes.
And then, it was cooled to 60.degree. C. and mixed with
N,N-dimethylacetamide to obtain a solution having a solid content
of approximately 45%. Subsequently, the terminal-treated glycol was
allowed to react with diethylamine, ethylenediamine and
1,3-cyclohexylene diamine of molar ratio of 90/10 which are a chain
extender at temperature of approximately 75.degree. C. for 2-3
minutes while vigorously agitating. Molar ratio of the diamine
chain extender with respect to diethylamine was 6.3, and an
unreacted segmented polyurethane in the glycol terminal-treated by
the diamine chain extender contained approximately 36% of solid and
showed a viscosity of approximately 2100 poise at 40.degree. C. A
variety of additives were dispersed in dimethylacetamide which is a
solvent, followed by completely mixing with a polymer solution to
prepare a solution containing a solid content of 2% of the
copolymers 1-6 obtained in the Examples 5-1 to 5-6, 3% of zinc
oxide, 1.5% of "Syanox" 1790 which is a sterically-hindered
phenol-based anti oxidant
[2,4,6-tris(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)isocyanurate],
and 0.01% of a silicone oil in a final film. Herein, all the
concentration is based on the weight of spandex polymer. A film of
thus-prepared solution was cast, and washed by the water-based
solvent described hereinabove before a test. Efficiency of heat-set
was measured, and results are collectively shown in Table 5-1.
TABLE 5-1 Example Comparative Example 1 2 3 4 5 6 1 2 Initial Feed
25 25 25 25 25 25 25 25 DMAc Dropping composition DMAc 15.4 15.4
15.4 15.4 15.4 15.4 15.4 15.4 ABN-E 0.675 0.675 0.300 0.675 0.675
0.675 0.675 0.675 DIPAM 45 45 45 45 45 DEAM 45 DMAM 45 DMAA 45
PCL-FM2D 15 7.5 15 15 15 15 n-decyl-MA 15 lauryl-MA 7.5 15 Delayed
Feed ABN-E 0.675 0.675 0.675 0.675 0.675 0.675 0.675 0.675 N.V. (%)
57.1 58.3 57.8 56.9 59.7 58.2 57.7 58.8 Mn 13700 12500 14000
THF-based: THF-based: THF-based: 14500 12700 incapable of incapable
of incapable of measuring measuring measuring by GPC by GPC by GPC
Mw 46100 33800 246000 32700 29800 Mw/Mn 3.36 2.70 17.6 2.26 2.34
Example Comparative Example 7 8 9 10 11 12 3 4 Solubility to
Excellent Excellent Excellent Excellent Excellent Excellent Bad Bad
DMAc HSE (more than 82 80 85 78 76 75 80 81 70%:excellent) DIPAM:
Diisopropyl aminoethylmethacrylate DMAC: Dimethylacetoamide DEAM:
Diethyl aminoethylmethacrylate DMAM: Dimethyl
aminoethylmethacrylate DMAA: Dimethyl aminoethylacrylate HSE:
Heat-set efficiency
Even in the all experiments, excellent results were obtained.
The above-described results in the Examples show an advantageous
effect which affects to an excellent solubility to a solvent and
heat-set efficiency in the case that the additives which are a
copolymer of a dialkyl aminoethyl(meth)acrylate with a
monomethacrylate of .epsilon.-caprolactone-modified ethyleneglycol
is added to a spandex.
Possibility of Utilization in Industry
As being clear from the above-described results in the Examples,
since a polyurethane elastic fiber having an excellent hydrolysis
resistance in alkali and a high tensile strength property can be
obtained according to the present inventions No. 1, 2, and 3, it
can largely contribute to an industrial field.
As being clear from the above descriptions, since a polyurethane
elastic fiber having an excellent weatherability and an excellent
washing resistance can be obtained according to the present
invention No. 4, it can largely contribute to an industrial
field.
The novel dialkylamino group-contained acrylic-based copolymer
which is the present invention No. 5 shows a higher solubility to
DMAC which is a solvent, and it protects a polyurethane and a
spandex polymer from deterioration and discoloration. In a
polyurethane composition and a spandex composition which contain
the copolymer, a decrease of elasticity is improved in relation to
the use of an already-known high molecular weight tertiary amino
group-contained additive having a steric hindrance, and it has an
excellent permanent extension property.
An excellent artificial leather can be obtained by the use of a
polyurethane prepared using a specified polyester diol in the
present invention No. 6.
* * * * *